Chemoselective Transesterification of Methyl (Meth)acrylates Catalyzed by Sodium(I) or Magnesium(II) Aryloxides

Ng, Jie Qi; Arima, Hiro; Mochizuki, Takuya; Toh, Kohei; Matsui, Kai; Ratanasak, Manussada; Hasegawa, Jun‐ya; Hatano, Manabu; Ishihara, Kazuaki

doi:10.1021/acscatal.0c04217

Cited by 15 publications

(25 citation statements)

References 56 publications

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“…Reports in the patent literature , describe NaBHT preparation from NaOH in boiling xylenes with azeothropic distillation. A few sources report the preparation of NaBHT from NaOMe either in methanol ,,, or in a heated aromatic hydrocarbon . MeOH remains as a solvate in NaBHT when prepared by this method, , which requires high-temperature drying for its removal .…”

Section: Resultsmentioning

confidence: 99%

“…A few sources report the preparation of NaBHT from NaOMe either in methanol ,,, or in a heated aromatic hydrocarbon . MeOH remains as a solvate in NaBHT when prepared by this method, , which requires high-temperature drying for its removal . As MeOH is known to reduce catalytic Pd(II) intermediates to Pd(I) species, it is not the right solvent choice for Pd-catalyzed processes.…”

Section: Resultsmentioning

confidence: 99%

“…All three properties make it useful for Pd-catalyzed C−N coupling reactions. 3−5 It has also been applied in coordination chemistry, 6−26 as a CO 2 carrier in carboxylation 27−34 and decarboxylation 35 reactions, and as a catalyst in transesterification, 36 lactide polymerization, 37 and acrylate arylation. 38 Traditionally, NaBHT is generated ex situ by the reaction of BHT (2,6-di-tert-butyl-4-methylphenol) with either NaH [3][4][5]27,39,40 or metallic Na (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

“…NaBHT (sodium 2,6-di- tert -butyl-4-methylphenoxide, Scheme ) is a non-nucleophilic base of medium strength (conjugated acid p K a 12.58 in water, 17.7 in DMSO) that is very lipophilic and soluble in most organic solvents. All three properties make it useful for Pd-catalyzed C–N coupling reactions. − It has also been applied in coordination chemistry, − as a CO 2 carrier in carboxylation − and decarboxylation reactions, and as a catalyst in transesterification, lactide polymerization, and acrylate arylation . Traditionally, NaBHT is generated ex situ by the reaction of BHT (2,6-di- tert -butyl-4-methylphenol) with either NaH − ,,, or metallic Na (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

“… ,,,,− ,− , Despite its wide application scope, the structure of NaBHT has not been rigorously investigated. NMR spectra have been reported for DMSO- d 6 , THF, and MeOH solvates, and an SC-XRD structure was published only for the THF solvate . That said, little is known about the solvation of NaBHT in different solvents and in the solid state, and the lability of solvent molecules bound to Na has not been assessed.…”

Section: Introductionmentioning

confidence: 99%

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NaBHT Generated In Situ from BHT and NaOtBu: Crystallographic Characterization and Applications in Buchwald–Hartwig Amination

et al. 2021

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NaBHT is a valuable medium-strength base useful for many applications, particularly for Buchwald–Hartwig coupling. The structures of solvent-free NaBHT and its solvates with Et2O, THF, tBuOH, and a THF/tBuOH mixture were established using single-crystal X-ray diffraction. While [NaBHT·Et2O]2 adopts a dimeric structure and crystallizes in a monoclinic cell, [NaBHT·THF]3, [NaBHT·tBuOH]3, and [NaBHT·(THF-tBuOH)]3 prefer a trimeric structure and crystallize in cubic cells. Solvent-free [NaBHT] n is different from solvated NaBHT and from other known sodium phenolates. It is an inorganic polymer that crystallizes in an orthorhombic cell, with a NaO core spreading in the [1 0 0] direction. Agostic interactions of the tBu group hydrogens with Na, which were confirmed for all structures, may help explain the reductive properties of NaBHT. Further, interactions of BHT with tBuONa in solution and in the solid state were examined, reveraling that NaBHT does not need to be prepared from pyrophoric NaH or metallic Na every time. Instead, it can be generated efficiently in or ex situ using NaOtBu in solution or with only a stoichiometric amount of solvent to assist in bringing the reactants together. Application of this methodology was demonstrated with the efficient, solvent-free, and Pd-catalyzed C–N coupling with Pd(NHC) catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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NaBHT Generated In Situ from BHT and NaOtBu: Crystallographic Characterization and Applications in Buchwald–Hartwig Amination

et al. 2021

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Repeatedly Recyclable 3D Printing Catalyst‐Free Dynamic Thermosetting Photopolymers

et al. 2023

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and rapid prototyping, which has been widely used in myriad of areas, such as lightweight engineering, [4] sensors, [5] the biomedical, [6] flexible electronics [7] and others. [8] Recently, photocuring based 3D printing technologies, which include stereolithography (SLA), [9] digital light processing (DLP), [10] continuous liquid interface production (CLIP), [11] high-area rapid printing (HARP) [12] and two-photon polymerization (TPP), [13] have been drawing great attention in many fields due to their high resolution and printing efficiency properties. [14] Photopolymers, which combine the on-demand, light-triggered fabrication and the robust properties of crosslinked structures, are key materials for 3D printing technologies, especially for photo-curing based 3D printing technology. [15] The demand for 3D printing materials is growing along with the rapidly developing 3D printing industry. [16] However, the chemical cross-linking network makes photopolymers impossible or difficult to reprocess and reuse. [3a,17] Recent advances in the development of covalent adaptable networks (CANs) promote the creating recyclable photopolymers by incorporation of dynamic covalent bonds (DCBs) into structures. [18] Among all the photopolymers, acrylate-based inks or resins exhibit the high-speed of manufacturing and tunable mechanical properties, dominating the photo-resin market of the photocurable 3D printing industry. [19] Thus, the development of acrylate-based CANs photopolymers for 3D printing is of great importance. [20] This approach is exemplified by the work from Zhang and co-workers, [21] who immobilized dynamic hydroxyl-ester bonds into the photopolymers and developed a type of photocurable CANs, which is not only compatible with DLP-based 3D printing, but also reprocessable through bond-exchange reactions. However, the recycling strategy was limited to the traditional hot-pressing approach in this work. To realize the cyclical 3D printing, CANs were crushed and ground into powder or were depolymerized into soluble oligomers assisted with small molecules, and then were formulated with fresh photopolymers for the next round of printing. [22] Notably, in these examples, recovery of photopolymers using CANs generally requires a highly loaded catalyst to activate the dynamic bonds to change the topology, which may be poorly dispersed in the matrix and toxic, leading to poor homogeneity and toxicity of resin materials. [18a,23] Moreover, the recycled materials are usually used as fillers, Photo-curing 3D printing technology has promoted the advanced manufacturing in various fields, but has exacerbated the environmental crisis by the demand for the chemically cross-linked thermosetting photopolymers. Here, the authors report a generic strategy to develop catalyst-free dynamic thermosetting photopolymers, based on photopolymerization and transesterification, that can enable users to realize repeatable 3D printing, providing a practical solution to the environmental challenges. That the β-carbonyl group adjacent t...

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Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Lemouzy

Cuminet

Berne

et al. 2022

Chemistry A European J

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Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass‐like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst‐free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α‐ or β‐position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.

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Chemoselective Transesterification of Methyl (Meth)acrylates Catalyzed by Sodium(I) or Magnesium(II) Aryloxides

Cited by 15 publications

References 56 publications

NaBHT Generated In Situ from BHT and NaOtBu: Crystallographic Characterization and Applications in Buchwald–Hartwig Amination

NaBHT Generated In Situ from BHT and NaOtBu: Crystallographic Characterization and Applications in Buchwald–Hartwig Amination

Repeatedly Recyclable 3D Printing Catalyst‐Free Dynamic Thermosetting Photopolymers

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

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